Adhesive

ABSTRACT

An adhesive composition includes a polymer adhesive material and a thickener. The adhesive composition has a stringing length of 9 cm or less and a phase lag of 45 degrees or less or a sag distance of 5 mm or less. The adhesive can be formed by combining a vinyl acetate polymer, an alkali swellable thickener, an alkali material, and water.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from provisional U.S. Application No.60/530,591, filed Dec. 18, 2003 entitled CRAFT OBJECTS.

BACKGROUND

This invention relates to improved adhesives. Specifically, theinvention relates to improved adhesives that exhibit improveddispensability properties.

Typical consumer adhesives or white glues are formulated at 40 to 60percent solids and have a viscosity ranging from 2,000 to 300,000 cP asmeasured by on a Brookfield viscometer. These adhesives or white glueshave a variety of shortcomings such as, for example, regardless ofviscosity, the glues run or sag when applied to a vertical surface. Inaddition, these glues suffer from imprecise dispensability. Lowviscosity glues are excessively runny and high viscosity glues areexcessively stringy.

In general, the more viscous glues tend to be slow to “set” and aredifficult to obtain in thin sections since they do not spread easilyunder modest stress. Thick glue sections can be undesirable since upondrying, they exacerbate curl and cockle effects in paper substrates.Thus, there is a need for an improved adhesive.

SUMMARY

Generally, the present invention relates to improved adhesives, theirmanufacture, and apparatus for dispensing the improved adhesive. In anillustrative embodiment, an adhesive composition includes a polymeradhesive material and a thickener. The adhesive composition has astringing length of 9 cm or less and a phase lag, δ, (hereinafterreferred to as “phase lag”) of 45 degrees or less, or a sag distance of5 mm or less. The adhesive can be formed by combining a vinyl acetatepolymer, an alkali swellable thickener, an alkali material, and water.

In another illustrative embodiment, an article includes a dispensercontainer having a dispensing opening and an adhesive compositiondisposed within the dispenser container. The adhesive compositionincludes a polymer adhesive material and a thickener. The adhesivecomposition has a stringing length of 9 cm or less and a phase lag of 45degrees or less.

In another illustrative embodiment, an adhesive composition includes avinyl acetate polymer, an alkali swellable thickener, and water. Thevinyl acetate polymer is dispersed within the water and the adhesivecomposition has a pH of 4 to 10.

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The Figures, Detailed Description and Examples which followmore particularly exemplify these embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention may be more completely understood in consideration of thefollowing detailed description of various embodiments of the inventionin connection with the accompanying drawings, in which:

FIG. 1 is a schematic view of an illustrative adhesive dispenser.

While the invention is amenable to various modifications and alternativeforms, specifics thereof have been shown by way of example in thedrawings and will be described in detail. It should be understood,however, that the intention is not to limit the invention to theparticular embodiments described. On the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention.

DETAILED DESCRIPTION

The present invention is believed to be applicable generally toadhesives and their manufacture, as well as apparatus for dispensingsuch improved adhesives. While the present invention is not so limited,an appreciation of various aspects of the invention will be gainedthrough a discussion of the examples provided below.

For the following defined terms, these definitions shall be applied,unless a different definition is given in the claims or elsewhere inthis specification.

The term “polymer” will be understood to include polymers, copolymers(e.g., polymers formed using two or more different monomers), oligomersand combinations thereof, as well as polymers, oligomers, or copolymersthat can be formed in a miscible blend by, for example, coextrusion orreaction, including transesterification. Both block and randomcopolymers are included, unless indicated otherwise.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the specification and claims are to be understoodas being modified in all instances by the term “about.” Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe foregoing specification and attached claims are approximations thatcan vary depending upon the desired properties sought to be obtained bythose skilled in the art utilizing the teachings of the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques. Notwithstanding that the numerical ranges and parameterssetting forth the broad scope of the invention are approximations, thenumerical values set forth in the specific examples are reported asprecisely as possible. Any numerical value, however, inherently containscertain errors necessarily resulting from the standard deviations foundin their respective testing measurements.

Weight percent, percent by weight, % by weight, and the like aresynonyms that refer to the concentration of a substance as the weight ofthat substance divided by the weight of the composition and multipliedby 100.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5).

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” include plural referents unless the contentclearly dictates otherwise. Thus, for example, reference to acomposition containing “a compound” includes a mixture of two or morecompounds. As used in this specification and the appended claims, theterm “or” is generally employed in its sense including “and/or” unlessthe content clearly dictates otherwise.

The present invention provides an improved adhesive. The improvedadhesive includes a polymer adhesive material, and a thickener. Theimproved adhesive has two or more of the following physical properties:a limited stringing length; a limited phase lag; a limited sag distance;a viscosity such that the adhesive is flowable; a limited set time; arange of complex shear modulus; and the adhesive composition may not bethixotropic. Many of these properties can be determined by the methodsset in the Methods section below.

The adhesive composition can have a limited stringing length. Stringinglength of an adhesive can be determined by the stringing length methoddefined in the Methods section below. A limited stringing length can aidin precise placement of flowable adhesives. In some embodiments, theadhesive composition can have a stringing length of 0 to 9 cm, or 0 to 5cm, 0 to 3 cm, or 0 to 2 cm.

The adhesive composition can have a limited shear modulus phase lag.Shear modulus phase lag or “phase lag,” can be determined by the phaselag method defined in the Methods section below. In some embodiments,the adhesive composition can have a phase lag of 0 to 45 degrees, or 0to 30 degrees, or 0 to 20 degrees.

The adhesive composition can have a limited sag distance when placed ona vertical surface. Sag distance or sag resistance can be determined bythe sag distance method defined in the Methods section below. A limitedsag distance can aid in keeping adhesive on a surface where it isplaced. In some embodiments, the adhesive composition can have a sagdistance of 0 to 10 mm, or 0 to 5 mm, or 0 to 2 mm.

The adhesive composition can have a viscosity such that the adhesive isflowable. Viscosity can be determined via a Brookfield RVT with a #6spindle at 20 rpm at ambient conditions. In some embodiments, theadhesive composition can have a viscosity of 3,000 to 50,000 cP, or3,000 to 30,000 cP, or 10,000 to 30,000 cP.

The adhesive composition can have a limited set time. Set time of theadhesive can be determined by the set time method defined in the Methodssection below. In some embodiments, the adhesive composition can have aset time of 0 to 180 seconds, or 0 to 60 seconds, or 0 to 45 seconds.

The adhesive composition can have a range of complex shear modulus G*.Complex shear modulus G* can be determined by the complex shear modulusmethod defined in the Methods section below. In some embodiments, theadhesive composition can have a complex shear modulus G* of 50 to 1000Pa, or 100 to 600 Pa.

In some embodiments, the adhesive composition includes a polymeradhesive material and a thickener where the adhesive composition has astringing length of 9 cm or less and a phase lag of 45 degrees or less.In another embodiment, the adhesive composition includes a polymeradhesive material and a thickener where the adhesive composition has astringing length of 9 cm or less and a sag distance of 10 mm or less. Inother embodiments, two or more of the above identified physicalproperties can be combined, as desired.

The improved adhesive composition can be formed by combining an adhesivepolymer, a thickener, and water. The adhesive polymer can be a vinylacetate polymer. The thickener can be an alkali swellable thickener. Insome embodiments, the adhesive composition can have a glass transitiontemperature in a range of −60 to 100 degrees Celsius; or, −50 to 50degrees Celsius, −20 to 30 degrees Celsius. As used herein, glasstransition temperatures of the adhesive composition are taken from driedadhesive compositions. In illustrative embodiments, the adhesivecomposition can have a total solids content from 5 to 85 wt %, or 30 to85 wt %, or 60 to 80 wt %, as desired.

In some illustrative embodiments, the adhesive composition can have a pHof 4 to 10, or 5 to 10, or 6 to 9. In other embodiments the adhesivecomposition can be considered as being “acid-free” and have a pH of 7 to9. In some embodiments, an alkali or alkaline material can be added tothe adhesive composition in any useful amount.

Vinyl acetate polymers include, for example, vinyl acetate homopolymersand vinyl acetate co-polymers such as, for example, vinylacetate-ethylene (VAE). These vinyl acetate polymers can be combined inwater to form a polymer dispersion. Vinyl acetate based polymers can beobtained by conventional emulsion polymerization and are commerciallyavailable from a variety of sources.

One or more co-monomers can be co-polymerized with vinyl acetate. Insome embodiments, the vinyl acetate polymer includes vinyl acetate,ethylene, and optionally one or more other ethylenically unsaturatedmonomers. Illustrative examples of other ethylenically unsaturatedmonomers are C₃-C₁₀ alkenoic acids, such as acrylic acid, methacrylicacid, crotonic acid and isocrotonic acid and their esters with C₁-C₁₈alkanols, such as methanol, ethanol, propanol, butanol, and2-ethylhexanol; vinyl halides, such as vinyl chloride; alpha,beta-unsaturated C₄-C₁₀ alkenedioic acids such as maleic acid, fumaricacid, and itaconic acid and their monoesters and diesters with the sameC₁-C₁₈ alkanols; and nitrogen containing monoolefinically unsaturatedmonomers, such as nitriles; arnides; N-methylol amides; lower alkanoicacid ethers of N-methylol amides and allylcarbamates, such asacrylonitrile, acrylanide, methacrylamide, N-methylol acrylamide,N-methylol methacrylamide, N-methylol allylcarbamate, and lower alkylethers or lower alkanoic acid esters of N-methylol acrylamide,N-methylol methacrylamide and N-methylol allylcarbamate. Illustrativevinyl acetate-ethylene (emulsion) polymers used in this invention arecommercially available products. Examples are AIRFLEX™ 320, AIRFLEX™323, AIRFLEX™ 400, AIRFLEX™ 400H, AIRFLEX™ 401, AIRFLEX™ 405, AIRFLEX™410, AIRFLEX™ 420, AIRFLEX™ 423, AIRFLEX™ 426, AIRFLEX™ 460, AIRFLEX™465, AIRFLEX™ 7200, AIRFLEX™ 920, AIRFLEX™ EN421, AIRFLEX™ EP17,AIRFLEX™ 315, AIRFLEX™ 418, AIRFLEX™ EF350, and AIRFLEX™ EF940, allavailable from Air Products Polymers, L.P., (Allentown, Pa.) and ELVACE™722, ELVACE™ 725, ELVACE™ 731, ELVACE™ 732, ELVACE™ 733, ELVACE™ 734,ELVACE™ 735, ELVACE TM 736, ELVACE™ 737, ELVACE™ 739, ELVACE™ 741, andELVACE™ 758 available from Forbo Adhesives, LLC (Durham, N.C.) andDUR-O-SET™ E-200, DUR-O-SET™ E-200, DUR-O-SET™ E-230, DUR-O-SET™ E-130,DUR-O-SET™ E-200HV, DUR-O-SET™ E-150, DUR-O-SET™ E-260, DUR-O-SET™E-100, DUR-O-SET™ E-220, DUR-O-SET™ E-171HS, DUR-O-SET™ C-325,DUR-O-SET™ C-310, DUR-O-SET™ C-335, RESYN™ 1025, RESYN™ 1072, RESYN™1601, and RESYNT™ SB-321 available from Vinamul Polymers, (Enoree, S.C.)and WB-3621, WB-3621 available from H.B. Fuller Co. (St Paul, Minn.).Commercially available vinyl acetate polymers, as provided, typicallycan have a viscosity ranging from 500 to 3000 cP.

Vinyl acetate polymers can be present in the adhesive compositions inany useful amount. In some embodiments, vinyl acetate polymers arepresent in the adhesive composition from 5 to 75 wt %, or from 20 to 75wt %, or 50 to 75 wt %, as desired.

Alkali swellable thickeners include alkali swellable acrylic thickeners.These acrylic thickeners can be termed an “associative thickener” andcan be anionic alkali swellable acrylic aqueous emulsion copolymerscontaining carboxylic acid groups. These alkali swellable thickeners canbe substantially cross-linked. A partial listing of suitable alkaliswellable acrylic thickeners includes those commercially available underthe trade name Rhoplex™ ASE-60, from Rohm and Haas Co. (Philadelphia,Pa.) and Rohagit™ SD 15 available from Polymer Latex GmbH & Co. KG,(Marl, Del.) and Carbopol™ and Pemulen™ series thickeners from Noveon,Inc (Cleveland, Ohio).

Alkali swellable thickeners can be present in the adhesive compositionsin any useful amount. In some embodiments, Alkali swellable thickenersare present in the adhesive composition from 0.1 to 10 wt %, or from 0.1to 5 wt %, or 0.1 to 3 wt %, as desired.

An alkali material or alkalinity source can be combined with the alkaliswellable thickener during the formation of the adhesive composition.The alkalinity source can be a strong base material or a source ofalkalinity which can be an organic source or an inorganic source ofalkalinity. For the purposes of this invention, a source of alkalinityalso known as an alkali material is a composition that can be added toan aqueous system and result in a pH greater than about 7. Organicsources of alkalinity are often strong nitrogen bases including, forexample, ammonia, monoethanol amine, monopropanol amine, diethanolamine, dipropanol amine, triethanol amine, tripropanol amine, etc. Thesource of alkalinity can also comprise an inorganic alkali. Theinorganic alkali can be derived from sodium or potassium hydroxide whichcan be used in both liquid (about 10-60 wt % aqueous solution) or insolid (powder, flake or pellet) form. Other inorganic alkalinity sourcesare soluble silicate compositions such as sodium metasilicate or solublephosphate compositions such as trisodium phosphate, or any other bufferderived from phosphoric acid. Exemplary alkalinity sources includeammonia, or triethanol amine. The alkalinity source can include analkali metal carbonate. Alkali metal carbonates which may be usedinclude sodium carbonate, potassium carbonate, sodium or potassiumbicarbonate or sesquicarbonate, among others. The alkali material can beprovided in the adhesive composition in any useful amount.

The adhesive compositions of the invention can optionally includefillers. Fillers can be organic or inorganic fillers and can be presentin the adhesive in any useful amount. Fillers can be any organic orinorganic additives such as, for example, antioxidants, stabilizers,antiozonants, plasticizers, dyes, U.V. absorbers, HALS, and pigments. Inone embodiment, the adhesive composition includes a “glitter” materialas a filler. The glitter material can add sparkle and/or color to theadhesive as desired. The adhesive compositions of the invention canoptionally include colorants, such as pigments or dyes, to provide atint or color to the adhesive composition.

In some embodiments, the adhesive composition can include 5 to 75 wt %vinyl acetate polymer, 0.1 to 10 wt % alkali swellable thickener, and abalance water. In other embodiments, the adhesive composition caninclude 20 to 75 wt % vinyl acetate polymer, 0.1 to 5 wt % alkaliswellable thickener, and a balance water. In other embodiments, theadhesive composition can include 50 to 75 wt % vinyl acetate polymer,0.1 to 3 wt % alkali swellable thickener, and a balance water. In someof these embodiments, the formation of the adhesive composition caninclude the addition of an alkali material that may activate or swellthe alkali swellable thickener material and provide a resulting adhesivecomposition that can have a pH of 7 to 9. In illustrative embodiments,the alkali swellable thickener material is substantially cross-linked.These embodiments can possess two or more of the following physicalproperties (as described above): a limited stringing length; a limitedphase lag; a limited sag distance; a viscosity such that the adhesive isflowable; a limited set time; a range of complex shear modulus; and theadhesive composition may not be thixotropic.

FIG. 1 shows an illustrative adhesive dispenser 100 that can hold anddispense the improved adhesive described herein. The dispenser 100 caninclude an adhesive containing portion 120 that contains the adhesiveprior to being dispensed. In some embodiments, the containing portion120 is formed of a flexible material such as a polymeric material. Thedispenser can contain any useful amount of adhesive such as, forexample, 0.5 to 5000 ml, or 0.5 to 1000 ml, or 50 to 500 ml. Thedispenser 100 can include a dispensing portion 130 disposed on thecontaining portion 120. The dispensing portion 130 can include adispenser opening 140. In one embodiment, adhesive can be dispensed by auser by the user applying finger pressure to the flexible containingportion 120 which urges adhesive material toward and through thedispenser opening 140 to the application target. In some embodiments,the dispenser opening 140 has an area in a range of 0.05 to 40 mm², 0.1to 30 mm², 0.1 to 10 mm², 0.2 to 1.8 mm², 0.5 to 1.5 mm², or 0.75 to1.25 mm², as desired.

Described herein are adhesive compositions exhibiting a uniquecombination of rheology and fast set time, and when applied to papersubstrates, can reduce the amount of curl/cockle observed. Theseadhesive compositions are easily and precisely dispensed from a finetipped applicator using only hand pressure to apply. Suchadhesive/dispenser combinations are often used in performing craftprojects, household repairs, or scrapbooking activities.

The combination of adhesive rheology and fine tipped dispensers providesexcellent control during adhesive dispensing and allows the user toeffortlessly apply the adhesive in any shape desired (fine or coarsedots, streaks, lines, etc). The adhesive rheology can also assist in thecreation of thin bond lines due to the ease with which the adhesivespreads when compressed lightly between adherents with modest laminationpressure, e.g., light hand pressure used to laminate paper card stocktogether. Such thin adhesive bond lines can also contribute to fastadhesive drying since the thin cross-sectional area of the adhesiveincreases the rate at which moisture is removed from the adhesive. Inaddition the rheology provided by associative thickened adhesivepolymers described herein also minimizes/eliminates the tendency of theadhesive to string or leg when applied in small drops or in a finecontinuous bead, thus allowing more precise application of the adhesive.

Advantages of the invention are illustrated by the following examples.However, the particular materials and amounts thereof recited in theseexamples, as well as other conditions and details, are to be interpretedto apply broadly in the art and should not be construed to unduly limitthe invention.

Methods

Set Time

This test involves the following steps:

-   1. Coat a stripe (5-10 cm wide) of adhesive (˜3 grams) onto a first    sheet of test paper (6″ wide IP Thilmany 50# Bleached Andro Base    Paper) to obtain a 0.23 mm thick wet adhesive coating;-   2. While adhesive is wet, laminate a second sheet of the test paper,    which has been pre-cut into 0.5″ width strips, to the first sheet of    test paper;-   3. Laminate the two sheets together by rolling with a 4.5 lb rubber    roller; and-   4. Peel the 0.5″ width paper strips from the laminate at regular    time intervals to determine how long it takes to develop sufficient    strength to tear the test paper strip.    Sag Resistance or Distance

Adhesive sag resistance is assessed by depositing a 0.1 ml drop ofadhesive near an end of a horizontally positioned 2 mil clean thickstrip of poly(ethylene terephthalate) (PET) film measuring ˜15 cm×25 cm.

Immediately following adhesive deposition, the PET film is positionedvertically, with the adhesive drop located at the top of sheet, whichallows the adhesive to flow downward along the length of the film strip.

When adhesive flow has ceased, the distance, in millimeters (mm), theadhesive has flowed is measured and recorded. The specific distancemeasured is that distance from the bottom edge of the original adhesivedrop, prior to orienting vertically, to the bottom most edge of theadhesive flow once the adhesive flow has ceased.

Stringing Length

This test method provides a means of assessing the extent to which anadhesive strings when dispensed. In general the test method involvesdispensing glue through a vertically oriented syringe needle at fixedrate, and measuring the length of the glue fiber/strand that forms asthe glue extends from the needle and falls to a stage below.

The longer the strand the higher the extent of stringing, the shorterthe strand the lower the extent of stringing. This test method isconducted in a constant temperature room having temperature of 22° C.and a relative humidity of 50% and employs the following equipment.

-   1. Syringe pump, catalog # 55-2226, Harvard Apparatus, So Natick,    Mass. 01760-   2. 16 ga×38 mm PrecisionGlide™ Needle 16G 1½ disposable syringe    needle, 1.19 mm ID, Becton Dickinson & Co, Franklin Lakes, N.J.    07417-1884-   3. 10 ml Luer Norm-Ject disposable syringe, Henke Sass Wolf GMBH,    Tuttlingen, Germany-   4. Teflon tubing 3.2 mm ID×152 mm length fit with male/female Luer    connections on opposite ends to provide a flexible connection    between the syringe and the needle-   5. Laboratory jack-   6. Laboratory jack stand-   7. Small laboratory clamp-   8. Cylindrical sleeve constructed from 0.45 mm thick clear    polycarbonate ˜14 cm dia×38 cm tall and slotted appropriately to    allow clearance for clamp and Teflon tubing clearance.    Equipment Preparation and Layout

The syringe/tubing/needle assembly is arranged with the syringe mountedhorizontally in the syringe pump and needle oriented vertically, suchthat the extruded adhesive discharges straight downward from the needletip.

The small clamp is affixed to the vertical member of the jack stand andthe needle is secured with the clamp to maintain orientation during thetest. The lab jack is placed on the jack stand below the needle toprovide a movable stage onto which the flowing adhesive impinges. Therange of lab jack motion is ˜38 cm total, i.e., the jack can be elevatedto touch the tip of the needle and can be lowered 38 cm below the tip ofthe needle.

The polycarbonate sleeve is used as a draft eliminator to reduce theeffect of any air motion on the falling strand of adhesive. The sleeveis placed on the jack such that it is concentric with the circumferenceof the needle barrel. Two longitudinal slots are required on the sleeveto allow the sleeve to pass by the small clamp and the flexible tubingas the lab jack is raised or lowered.

The needle was shortened, using a die grinder fit with cut-off wheel, toprovide a square end on the barrel of the needle and a length of 6.4 mm,i.e., 6.4 mm of needle protruded from the hub. The shortened needlebarrel was deburred with 320 grit sandpaper. The square-ended needlebarrel allows uniform discharge of the adhesive from the needle andminimizes any tendency for the extruded adhesive to drag or distort uponexiting the needle.

Testing Procedure

The adhesive is free of bubbles prior to performing this test. Thesyringe is filled with adhesive by immersing the syringe tip into theadhesive and gently withdrawing the plunger to fill the syringe. Caremust be taken during this operation to avoid introducing air into theadhesive as this deleteriously affects the test outcome, i.e., airbubbles in the discharged adhesive can cause flaws in the stream thatresult in premature breakage of the falling stream. The filled syringeis fit with the flexible connection tube and needle, and mounted in thesyringe pump. The pump is started to provide an adhesive flow of 1.75milliliters/minute (ml/min). The syringe needle is initially held byhand and oriented to discharge straight upward in order to purge any airfrom the flexible line, connections, or needle.

When a bubble free adhesive stream is observed exiting the needle thepump is stopped, the needle orientation reversed (to discharge straightdown), the needle clamped in position for testing, and the jack andcylindrical sleeve placed as described above.

To run the test the stage is positioned at a distance of 2.5 cm from theneedle tip, the pump started, and the adhesive stream observed. If theadhesive stream is stable and continuous the stage is slowly lowered in1 cm increments, with a 5 second observation time required at eachheight, until the stream breaks. The stage is then raised until the flowreconnects to provide a continuous stream. The stage is lowered in stepsto the point at which the stream breaks-off, and the distance at which acontinuous flow occurred is recorded (i.e., that distance from theneedle tip to the stage).

This protocol is repeated 2 more times to obtain a total of 3 separatemeasurements of the maximum distance at which a continuous strand couldbe observed. If upon starting the test the stream is discontinuous, thestage is raised to a point at which the flow connects to provide acontinuous stream and the protocol described above followed to completethe test. For certain adhesives, during the course of the test, thedispensed adhesive collecting on the stage may tend to pile up, thuswhen recording the maximum distance at which a continuous flow occurred,any buildup on the stage must be taken into account, i.e., the build-updistance (the height from the stage to the top of the adhesive pile)subtracted from the overall measured distance. The average of the threemeasurements is recorded as the “Continuous Fiber Stringing Length” andreported in centimeter units. If the test is not completed with aunitary syringe filling, the test can be restarted with another syringefilling at the preceding stage height and run to completion.

Shear Modulus (Phase Lag “δ” and Complex Shear Modulus “G*”)

Dynamic mechanical properties of the samples were measured with a BohlinCVO 120 HR NF rheometer. Bohlin rheometers are available from MalvernInstruments Ltd., Enigma Business Park, Grovewood Road, Malvern,Worcestershire, United Kingdom, WR14 1XZ. All measurements were takenusing the Bohlin C25 Mooney-Couette geometry at 25 degrees Celsius. Atrap was placed over the top of the C25 cup to retard sample drying.Evaporation traps are available from Malvern Instruments.

The dynamic mechanical properties of interest are the complex shearmodulus, G*, and the phase lag, which is also sometimes called phaseshift. These two parameters are often used to describe the relationshipbetween stress and strain for materials, and in particular forviscoelastic materials. Materials with high moduli provide greaterresistance to an applied stress, resulting in smaller strains, thanthose with low moduli. The phase lag is, by definition, bounded betweenzero and 90 degrees and represents the relative levels of elastic andviscous response of the sample to the applied stress. Purely elastic(i.e., Hookean) materials have a zero degree phase lag and purelyviscous materials have a 90 degree phase lag relative to the oscillatorystress.

G* and δ were measured by loading 17 grams of each sample into therheometer. The samples were equilibrated to 25° C., sheared for 30seconds at 50 s⁻¹, and then allowed to rest for 30 seconds before eachtest was run. Sinusoidally oscillating stresses were applied to eachsample at a frequency of 1 Hz. Ten stress amplitudes, increasinglogarithmically from 0.1 Pa to 100 Pa, were chosen as test conditions.The values of G* and δ at 1.7 Pa recorded by the instrument are usedhere.

EXAMPLES

Materials

-   Airflex™ 7200, VAE copolymer emulsion provided at ˜72.5% solids, pH    4.5-5.5, Tg 0° C., Air Products Polymers, L.P., Allentown, Pa.-   Airflex™ 465, VAE copolymer emulsion provided at ˜67% solids, pH    4.5-5.5, Air Products Polymers, L.P., Allentown, Pa.-   Elvace™ 737, VAE copolymer emulsion provided at 67-70% solids, pH    4-5, Forbo Adhesives, LLC, Durham, N.C. Rhoplex™ ASE-60, alkali    swellable associative thickener supplied at 28% solids, Rohm and    Haas Co., Philadelphia, Pa.-   Ammonium hydroxide, 28-30% NH3, EM Science, Gibbstown, N.J.-   Aleene's Fast Grab Tacky Glue™, Duncan Enterprises, Fresno, Calif.-   Aleene's Original Tacky Glue™, Duncan Enterprises, Fresno, Calif.-   Aleene's Quick Dry Tacky Glue™, Duncan Enterprises, Fresno, Calif.-   Elmer's Glue-All™, Elmer's Products, Inc., Columbus, Ohio.-   Kelzan™ S, xanthan gum, lot 40863A, CP Kelco U.S., Inc., San Diego,    Calif.-   Sodium carboxymethylcellulose (Na CMC), type 7H4XF, lot 83724,    Aqualon Division of Hercules Inc., Wilmington, Del.-   Kelgin™ MDH, sodium alginate, lot 281211, ISP Technologies Inc., San    Diego, Calif.-   Laponite™ RD, synthetic layered silicate, Southern Clay Products,    Inc., Gonzales, Tex.    General Preparation Procedure

The inventive adhesive examples described herein typically consist of anadhesive polymer, associative thickener, water, and base. Such samplesare prepared by combining the adhesive polymer, thickener, and water ina vessel and mixing well with a motor driven marine propeller to obtaina uniform composition. With continued stirring the base is added in asingle charge and agitation continued until the adhesive composition iswell mixed.

Examples 1, 2, 3, 5, 6, 7, 8

These Examples were prepared by the foregoing procedure and consisted ofthe materials and quantities (in grams) shown in Table 1. The resultingadhesives were characterized for Brookfield viscosity, set time,stringing, and rheology according to the test methods set forth above.The results are reported in Table 4.

TABLE 1 Adhe- sive Rhoplex ™ NH₄OH Sample Adhesive Amount ASE-60 Water(ml) Example 1 Airflex ™ 7200 200 2.0 — 0.7 Example 2 Airflex ™ 465 2002.5 — 0.7 Example 3 Elvace ™ 737 200 3.5 — 1.1 Example 5 Airflex ™ 7200100 0.5 — 0.35 Example 6 Airflex ™ 7200 100 4.63  45 0.51 Example 7Airflex ™ 7200 11.9 15 150 1.3 Example 8 Airflex ™ 7200 61.2 15 150 1.3

Example 4

A sample of Elvace™ 737 was neutralized as follows. To 175 parts Elvace™737 being agitated with a mechanical stirrer was added 0.56 ml NH₄OH.The pH of the well mixed solution was 7.63, as measured by a pH meter.To 100 parts of neutralized Elvace™ 737 being agitated with a mechanicalstirrer was added 2.67 parts Rhoplex™ ASE-60. After mixing well anadditional 0.25 parts NH₄OH solution was added and mixed in well tocomplete the preparation of Example 4 and provide an adhesive having pHof 7.12. Example 4 was characterized for Brookfield viscosity, set time,stringing, and rheology. The results are reported in Table 4.

Comparative Examples C4, C5, C6, C7

This series of comparative examples consisted of common commerciallyavailable consumer white glues listed in Table 2. These Examples werecharacterized for Brookfield viscosity, set time, stringing, andrheology. The results are reported in Table 4.

TABLE 2 Example Adhesive C4 Aleene's Fast Grab Tacky Glue ™ C5 Aleene'sOriginal Tacky Glue ™ C6 Aleene's Quick Dry Tacky Glue ™ C7 Elmer'sGlue-All ™

Comparative Examples C8, C9, C10, C11

This series of Comparative Examples employ as the adhesive neutralizedElvace™ 737 from Example 4. The adhesive, thickeners, and amounts ofeach are provided in Table 3. Samples were prepared by adding thethickener charge slowly to Elvace™ 737 that was agitated with amechanical stirrer and mixed for 15 minutes until the additive was wellincorporated. After standing for 24 hr some of the samples appeared tocontain small gel particles that could possibly be attributed tothickener that was either swollen or not completely dispersed initially.Each sample was mixed again for 15 minutes at which time all samplesappeared very smooth. Samples were additionally assessed for uniformityon a fineness of grind gauge (Precision Gage & Tool Co, Dayton, Ohio)which showed all to be smooth, uniform, and free of particulate. At thistime some of the samples had an additional charge of Elvace™ 737 addedto them and mixed in well as shown in Table 4. These Examples werecharacterized for Brookfield viscosity, set time, stringing, andrheology. The results are reported in Table 4.

TABLE 3 Comparative Elvace ™ Thickener Additional Example 737 TypeThickener Elvace ™ 737 C8  100 Kelzan ™ S 0.38 — C9  100 Na CMC 0.3124   C10 100 Kelgin ™ MDH 0.17 30.8 C11 100 Laponite ™ RD 0.50 71.8

TABLE 4 Shear Modulus² Brookfield Continuous Fiber Sag Distance G*, Paδ, deg Example Viscosity¹, cP Set Time, s Stringing Length, cm mm 1 Hz,1.7 Pa 1 Hz, 1.7 Pa 1 30000 48 2 2 542 13 2 23500 45 1 4 401 12 3 2350048 2 9 264 18 C1 3500 38 1 61 9 63 C2 2500 35 1 71 9 63 C3 3000 38 1 735 67 4 37000 58 9 3 896 16 5 8750 57 3 9 163 17 6 14750 72 2 0 490 11 710750 >240 2 5 270 8 8 13000 73 2 4 341 9 C4 195000 68 too visc tomeasure 22 705 77 C5 41500 85 27 33 192 82 C6 8500 63 5 68 34 80 C7 6000105 2 115 29 88 C8 22250 48 15 6 157 22 C9 25500 42 11 3 249 22  C1023750 53 12 6 314 24  C11 11500 45 10 0 194 15 ¹data taken withBrookfield RVT, spindle #6, 20 rpm, except C4 measured at 5 rpm

The complete disclosure of all patents, patent documents, andpublications cited herein are incorporated be reference. The foregoingdetailed description and examples have been given for clarity ofunderstanding only. No unnecessary limitations are to be understoodtherefrom. The invention is not limited to the exact details shown anddescribed, for variations obvious to one skilled in the art will beincluded within the invention defined by the claims.

1. An adhesive composition consisting of: a vinyl acetate-ethylene copolymer; an alkali swellable thickener; water; and a source of alkalinity; wherein the vinyl acetate-ethylene copolymer is dispersed within the water and the adhesive composition has a pH of 4 to 10; and wherein the adhesive composition has a stringing length of 9 cm or less, a set time of 180 seconds or less, and one or more of the following properties: a phase lag of 45 degrees or less; a viscosity of 3,000 to 50,000 cP; a complex shear modulus of 50 to 1000 Pa; and a sag distance of 10 mm or less.
 2. A adhesive composition according to claim 1, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 5 to 75 wt %.
 3. An adhesive composition according to claim 2, wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 10 wt %.
 4. An adhesive composition according to claim 1, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 20 to 75 wt %.
 5. An adhesive composition according to claim 4, wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 5 wt %.
 6. An adhesive composition according to claim 1, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 50 to 75 wt %.
 7. An adhesive composition according to claim 6, wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 3 wt %.
 8. An adhesive composition according to claim 1, wherein the alkali swellable thickener is an anionic alkali swellable acrylic thickener.
 9. An adhesive composition according to claim 1, wherein the composition has a total solids content of 5 to 85%.
 10. An adhesive composition according to claim 1, wherein the composition has a total solids content of 30 to 85%.
 11. An adhesive composition according to claim 1, wherein the composition has a total solids content of 60 to 80%.
 12. An adhesive composition according to claim 1, wherein the adhesive composition has a phase lag of 30 degrees or less.
 13. An adhesive composition according to claim 7, wherein the adhesive composition has a phase lag of 20 degrees or less.
 14. An adhesive composition according to claim 1, wherein the adhesive composition has a sag distance of 2 mm or less.
 15. An adhesive composition according to claim 1, wherein the adhesive composition has a sag distance of 5 mm or less.
 16. An adhesive composition according to claim 1, wherein the adhesive composition has a phase lag of 45 degrees or less, a viscosity of 3,000 to 50,000 cP, a complex shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm or less.
 17. An adhesive composition according to claim 1, wherein the source of alkaline material is selected from the group consisting of ammonia, triethanol amine, phosphates, and mixtures thereof.
 18. An adhesive composition consisting of: a vinyl acetate-ethylene copolymer; an alkali swellable thickener; water; a source of alkalinity; and one or more fillers; wherein the vinyl acetate-ethylene copolymer is dispersed within the water and the adhesive composition has a pH of 4 to 10; and wherein the adhesive composition has a stringing length of 9 cm or less, a set time of 180 seconds or less, and one or more of the following properties: a phase lag of 45 degrees or less; a viscosity of 3,000 to 50,000 cP; a complex shear modulus of 50 to 1000 Pa; and a sag distance of 10 mm or less.
 19. An adhesive composition according to claim 18, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 5 to 75 wt %.
 20. An adhesive composition according to claim 19 wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 10 wt %.
 21. An adhesive composition according to claim 18, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 20 to 75 wt %.
 22. An adhesive composition according to claim 21, wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 5 wt %.
 23. An adhesive composition according to claim 18, wherein the vinyl acetate-ethylene copolymer is present in the adhesive composition at 50 to 75 wt %.
 24. An adhesive composition according to claim 23, wherein the alkali swellable thickener is present in the adhesive composition at 0.1 to 3 wt %.
 25. An adhesive composition according to claim 18, wherein the alkali swellable thickener is an anionic alkali swellable acrylic thickener.
 26. An adhesive composition according to claim 18, wherein the composition has a total solids content of 5 to 85%.
 27. An adhesive composition according to claim 18, wherein the composition has a total solids content of 30 to 85%.
 28. An adhesive composition according to claim 18, wherein the composition has a total solids content of 60 to 80%.
 29. An adhesive composition according to claim 18, wherein the adhesive composition has a phase lag of 30 degrees or less.
 30. An adhesive composition according to claim 18, wherein the adhesive composition has a phase lag of 20 degrees or less.
 31. An adhesive composition according to claim 18, wherein the adhesive composition has a sag distance of 2 mm or less.
 32. An adhesive composition according to claim 18, wherein the adhesive composition has a sag distance of 5 mm or less.
 33. An adhesive composition according to claim 18, wherein the adhesive composition has a phase lag of 45 degrees or less, a viscosity of 3,000 to 50,000 cP, a complex shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm or less.
 34. The adhesive composition of claim 18, wherein the one or more fillers are selected from the group consisting of one or more antioxidant, one or more stabilizer, one or more antiozonant, one or more plasticizer, one or more dye, one or more U.V. absorber, one or more HALS, one or more pigment, and one or more glitter material.
 35. An adhesive composition according to claim 18, wherein the source of alkaline material is selected from the group consisting of ammonia, triethanol amine, phosphates, and mixtures thereof.
 36. An adhesive composition consisting of: one or more vinyl acetate-ethylene copolymers; one or more alkali swellable thickeners; water; one or more sources of alkalinity; and one or more fillers; wherein the vinyl acetate-ethylene copolymer is dispersed within the water and the adhesive composition has a pH of 4 to 10; and wherein the adhesive composition has a stringing length of 9 cm or less, a set time of 180 seconds or less, and one or more of the following properties: a phase lag of 45 degrees or less; a viscosity of 3,000 to 50,000 cP; a complex shear modulus of 50 to 1000 Pa; and a sag distance of 10 mm or less.
 37. An adhesive composition according to claim 36, wherein the adhesive composition has a phase lag of 45 degrees or less, a viscosity of 3,000 to 50,000 cP, a complex shear modulus of 50 to 1000 Pa, and a sag distance of 10 mm or less. 